WO2020211128A1 - Thermally activated delayed fluorescence material, preparation method therefor, and organic light-emitting diode device - Google Patents

Thermally activated delayed fluorescence material, preparation method therefor, and organic light-emitting diode device Download PDF

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WO2020211128A1
WO2020211128A1 PCT/CN2019/085649 CN2019085649W WO2020211128A1 WO 2020211128 A1 WO2020211128 A1 WO 2020211128A1 CN 2019085649 W CN2019085649 W CN 2019085649W WO 2020211128 A1 WO2020211128 A1 WO 2020211128A1
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thermally activated
activated delayed
compound
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light
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罗佳佳
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武汉华星光电半导体显示技术有限公司
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Definitions

  • the invention belongs to the technical field of electroluminescent materials, and particularly relates to a thermally activated delayed fluorescent material, a preparation method thereof, and an organic electroluminescent diode device.
  • OLED display panels have active light emission without backlight, high luminous efficiency, large viewing angle, fast response speed, large temperature adaptation range, relatively simple production and processing technology, and drive
  • the advantages of low voltage, low energy consumption, lighter and thinner, flexible display and huge application prospects have attracted the attention of many researchers.
  • the principle of the OLED device is that under the action of an electric field, holes and electrons are injected from the anode and the cathode respectively, through the hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer, respectively, to form excitons in the light emitting layer.
  • Exciton radiation attenuates luminescence.
  • organic electroluminescent materials have a great impact on the performance of the devices.
  • the light-emitting layer of an OLED device generally contains a host material and a guest material, and the light-emitting guest material that plays a leading role is very important.
  • the light-emitting guest materials used in early OLED devices were fluorescent materials. Since the ratio of singlet and triplet excitons in OLED devices is 1:3, the theoretical internal quantum efficiency (IQE) of OLED devices based on fluorescent materials is only It can reach 25%, which greatly limits the application of fluorescent electroluminescent devices. Due to the spin-orbit coupling of heavy atoms, heavy metal complex phosphorescent materials can simultaneously use singlet and triplet excitons to achieve 100% IQE.
  • the pure organic thermally activated delayed fluorescence (TADF) material has a molecular structure combining electron donor (D) and electron acceptor (A).
  • D electron donor
  • A electron acceptor
  • the molecule has a small minimum single triplet energy difference ( ⁇ E) ST ), so that the triplet excitons can return to the singlet state through the reverse intersystem crossing (RISC), and then through the radiation transition to the ground state to emit light, so that the singlet and triplet excitons can be used at the same time, and 100% can also be achieved IQE.
  • TADF materials For TADF materials, fast reverse intersystem crossing constant (k RISC ) and high photoluminescence quantum yield (PLQY) are necessary conditions for the preparation of high-efficiency OLED devices. At present, TADF materials with the above conditions are still relatively scarce compared to heavy metal Ir complexes.
  • the purpose of the present invention is to provide a thermally activated delayed fluorescent material, which has an ultra-fast reverse inter-system crossing rate and high luminous efficiency, is a TADF compound with significant TADF characteristics, and can be used as a guest material for the light-emitting layer of an organic electroluminescent diode .
  • Another object of the present invention is to provide a method for preparing a thermally activated delayed fluorescent material, which is easy to operate and has a high yield of the target product.
  • Another object of the present invention is to provide an organic electroluminescent diode device, which uses the thermally activated delayed fluorescent material as the guest material of the light-emitting layer, thereby improving the light-emitting efficiency of the device.
  • the present invention provides a thermally activated delayed fluorescent material, which has a chemical structure shown in the following formula 1:
  • R 1 represents a chemical group as an electron donor
  • R 2 represents a chemical group as an electron acceptor
  • the electron donor group R 1 is selected from any one of the following groups:
  • the electron acceptor group R 2 is selected from any one of the following groups:
  • the thermally activated delayed fluorescent material is compound 1, compound 2 or compound 3.
  • the structural formulas of compound 1, compound 2 and compound 3 are as follows:
  • the present invention also provides a method for preparing thermally activated delayed fluorescent material, and its chemical synthesis route is as follows:
  • X is a halogen group
  • R 2 represents a chemical group as an electron acceptor
  • the general structural formula of the electron-donor-containing compound is R 1 -H, wherein R 1 represents a chemical group as an electron donor.
  • the electron donor group R 1 is selected from any one of the following groups:
  • the electron acceptor group R 2 is selected from any one of the following groups:
  • the electron donor compound is 9,10-dihydro-9,9-dimethylacridine, phenoxazine or phenothiazine.
  • the present invention also provides an organic electroluminescent diode device, including a substrate, a first electrode provided on the substrate, an organic functional layer provided on the first electrode, and a second electrode provided on the organic functional layer ;
  • the organic functional layer includes one or more organic film layers, and at least one of the organic film layers is a light-emitting layer;
  • the light-emitting layer includes a mixed host material and a guest material, and the guest material is selected from one or more of the thermally activated delayed fluorescent materials as described above.
  • the light-emitting layer is formed by vacuum evaporation or solution coating.
  • the host material is mCBP.
  • the substrate is a glass substrate, the material of the first electrode is indium tin oxide, and the second electrode is a double-layer composite structure composed of a lithium fluoride layer and an aluminum layer;
  • the organic functional layer includes multiple organic film layers, the multilayer organic film layer includes a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, wherein the material of the hole injection layer is molybdenum trioxide
  • the material of the hole transport layer is TCTA
  • the material of the electron transport layer is TmPyPB.
  • the present invention has the following advantages and beneficial effects:
  • the thermally activated delayed fluorescent material of the present invention is a red TADF compound with lower single triplet energy level difference, ultrafast reverse intersystem crossing rate and high luminous efficiency, when it is used as a red light guest material
  • the light-emitting efficiency of the organic light-emitting display device can be improved.
  • the organic electroluminescent diode device based on the thermally activated delayed fluorescent material of the present invention has achieved very high device efficiency.
  • Figure 1 is a diagram of HOMO and LUMO energy levels of compounds 1-3 prepared in specific examples 1-3 of the present invention
  • Figure 2 is a photoluminescence spectrum of compound 1-3 prepared in specific examples 1-3 of the present invention in a toluene solution at room temperature;
  • Fig. 3 is a schematic diagram of the structure of the organic electroluminescent diode device of the present invention.
  • the synthetic route of target compound 1 is as follows:
  • the synthetic route of target compound 2 is as follows:
  • raw material 1 (2.68g, 5mmol), phenoxazine (1.10g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6 mmol), and then add sodium tert-butoxide (0.58 g, 6 mmol) into the glove box, and drive 40 mL of toluene previously dewatered and deoxygenated under an argon atmosphere, and react at 120° C. for 24 hours.
  • the synthetic route of target compound 3 is as follows:
  • raw material 1 (2.68g, 5mmol), phenothiazine (1.19g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6 mmol), and then add sodium tert-butoxide (0.58 g, 6 mmol) into the glove box, and drive 40 mL of toluene previously dewatered and deoxygenated under an argon atmosphere, and react at 120° C. for 24 hours.
  • Figure 1 shows the orbital arrangement of compound 1-3. It can be clearly seen from Figure 1 that the highest electron occupied orbital (HOMO) and lowest electron unoccupied orbital (LUMO) of compound 1-3 are arranged in In different units, complete separation is achieved, which helps to reduce the energy difference ⁇ EST between systems, thereby improving the ability of reverse intersystem crossing.
  • Figure 2 shows the photoluminescence spectra of Compound 1-3 in a toluene solution at room temperature. For compounds 1-3, the lowest singlet energy level S1 and the lowest triplet energy level T1 of the molecule were simulated and calculated.
  • Examples 1-3 The relevant data of Examples 1-3 are shown in Table 1. It can be seen from Table 1 that the ⁇ Est of all the compounds is less than 0.3ev, which achieves a small singlet and triplet energy level difference, and has an obvious delayed fluorescence effect.
  • PL Peak represents the photoluminescence peak
  • S1 represents the singlet energy level
  • T1 represents the triplet energy level
  • ⁇ EST represents the difference between the singlet and triplet energy levels.
  • OLED organic electroluminescent diode
  • the organic electroluminescent diode device using the thermally activated delayed fluorescent material of the present invention as the guest material of the light-emitting layer may include a substrate 9, an anode layer 1, a hole injection layer 2, and a cavity which are sequentially arranged from bottom to top.
  • the substrate 9 is a glass substrate
  • the material of the anode 1 is indium tin oxide (ITO)
  • the substrate 9 and the anode 1 together constitute ITO glass.
  • the material of the hole injection layer 2 is molybdenum trioxide (MoO 3 ), the material of the hole transport layer 3 is TCTA, and the material of the light-emitting layer is a mixture of the activated delayed fluorescent compound of the present invention and mCBP.
  • the material of the electron transport layer 5 is TmPyPB.
  • the cathode has a double-layer structure composed of a lithium fluoride (LiF) layer and an aluminum (Al) layer.
  • TCTA refers to 4,4',4”-tris(carbazol-9-yl)triphenylamine
  • mCBP refers to 3,3'-bis(N-carbazolyl)-1,1'-biphenyl
  • TmPyPB refers to 1,3,5-Tris(3-(3-pyridyl)phenyl)benzene.
  • the organic electroluminescent diode device can be manufactured according to a method known in the art, and the specific method is: sequentially vapor-depositing a 2nm thick MoO 3 film, a 35nm thick TCTA film, and mCBP on the cleaned ITO glass under high vacuum conditions Add activated delayed fluorescent compound, 40nm thick TmPyPB film, 1nm thick LiF film and 100nm thick Al film.
  • the device as shown in Figure 3 is made by this method, and the specific device structures are as follows:
  • ITO/MoO 3 (2nm)/TCTA(35nm)/mCBP Compound 1(20%40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
  • ITO/MoO 3 (2nm)/TCTA(35nm)/mCBP Compound 2(20%40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
  • ITO/MoO 3 (2nm)/TCTA(35nm)/mCBP Compound 3(20%40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
  • the current-brightness-voltage characteristics of devices 1-3 are completed by Keithley source measurement systems (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes, and the electroluminescence spectrum is measured by the French JY company SPEX CCD3000 spectrometer , All measurements are done in room temperature atmosphere.
  • the performance data of devices 1-3 are shown in Table 2 below.
  • CIEy is the y coordinate value of the standard CIE color space.
  • the present invention fine-tunes the structure of the electron donor, changes the electron donating ability of the electron donor, studies the influence of the strength of the electron donor on the material performance, and designs a thermal activation delay with significant TADF characteristics.
  • the fluorescent material realizes the adjustment of the luminescence spectrum of the material from orange-red light to deep red light; when the present invention further applies the thermally activated delayed fluorescent material to the guest material of an organic electroluminescent diode device, it can effectively improve the organic electroluminescence
  • the luminous efficiency of the light-emitting diode device, the organic electroluminescent diode device based on the thermally activated delayed fluorescent material of the present invention has a very high device efficiency.

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Abstract

The present invention relates to a thermally activated delayed fluorescence material, a preparation method therefor, and an organic light-emitting diode device. The structural general formula of the thermally activated activation delayed fluorescence material is shown by formula I, which is as follows: (I), wherein R1 represents a chemical group of an electron donor, and R2 represents a chemical group acting as an electron receptor. The thermally activated delayed fluorescence material of the present invention has an ultra-high reverse intersystem crossing rate and high light-emission efficiency, and is a red-light TADF material with significant TADF characteristics. When the thermally activated delayed fluorescence material is used as a light-emitting layer object material and applied to the organic light-emitting diode device, the light-emission efficiency of the organic light-emitting diode device can be effectively improved, and the organic light-emitting diode device based on the thermally activated delayed fluorescence material of the present invention has very high device efficiency.

Description

热活化延迟荧光材料及其制备方法与有机电致发光二极管器件Thermally activated delayed fluorescent material and preparation method thereof and organic electroluminescent diode device 技术领域Technical field
本发明属于电致发光材料技术领域，特别涉及一种热活化延迟荧光材料及其制备方法和有机电致发光二极管器件。The invention belongs to the technical field of electroluminescent materials, and particularly relates to a thermally activated delayed fluorescent material, a preparation method thereof, and an organic electroluminescent diode device.
背景技术Background technique
有机电致发光二极管(Organic Light-Emitting Diode，OLED)显示面板以其主动发光不需要背光源、发光效率高、可视角度大、响应速度快、温度适应范围大、生产加工工艺相对简单、驱动电压低、能耗小、更轻更薄、柔性显示等优点以及巨大的应用前景，吸引了众多研究者的关注。Organic Light-Emitting Diode (OLED) display panels have active light emission without backlight, high luminous efficiency, large viewing angle, fast response speed, large temperature adaptation range, relatively simple production and processing technology, and drive The advantages of low voltage, low energy consumption, lighter and thinner, flexible display and huge application prospects have attracted the attention of many researchers.
OLED器件的原理在于，在电场作用下，空穴和电子分别从阳极和阴极注入，分别通过空穴注入层、空穴传输层和电子注入层、电子传输层，在发光层复合形成激子，激子辐射衰减发光。The principle of the OLED device is that under the action of an electric field, holes and electrons are injected from the anode and the cathode respectively, through the hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer, respectively, to form excitons in the light emitting layer. Exciton radiation attenuates luminescence.
有机电致发光材料作为OLED器件的核心组成部分，对器件的使用性能具有很大的影响。OLED器件的发光层一般含有主体材料和客体材料，其中，起主导作用的发光客体材料至关重要。早期的OLED器件使用的发光客体材料为荧光材料，由于其在OLED器件中单重态和三重态的激子比例为1:3，因此基于荧光材料的OLED器件的理论内量子效率(IQE)只能达到25％，极大的限制了荧光电致发光器件的应用。重金属配合物磷光材料由于重原子的自旋轨道耦合作用，使得它能够同时利用单重态和三重态激子而实现100％的IQE。然而，通常使用的重金属都是铱(Ir)、铂(Pt)等贵重金属，并且重金属配合物磷光发光材料在蓝光材料方面尚有待突破。纯有机热活化延迟荧光(TADF)材料，具有电子给体(D)和电子受体(A)相结合的分子结构，通过巧妙的分子设计，使得分子具有较小的最低单三重能级差(ΔE ST)，这样三重态激子可以通过反向系间窜越(RISC)回到单重态，再通过辐射跃迁至基态而发光，从而能够同时利用单、三重态激子，也可以实现100％的IQE。 As the core component of OLED devices, organic electroluminescent materials have a great impact on the performance of the devices. The light-emitting layer of an OLED device generally contains a host material and a guest material, and the light-emitting guest material that plays a leading role is very important. The light-emitting guest materials used in early OLED devices were fluorescent materials. Since the ratio of singlet and triplet excitons in OLED devices is 1:3, the theoretical internal quantum efficiency (IQE) of OLED devices based on fluorescent materials is only It can reach 25%, which greatly limits the application of fluorescent electroluminescent devices. Due to the spin-orbit coupling of heavy atoms, heavy metal complex phosphorescent materials can simultaneously use singlet and triplet excitons to achieve 100% IQE. However, the commonly used heavy metals are precious metals such as iridium (Ir) and platinum (Pt), and the phosphorescent materials of heavy metal complexes still need a breakthrough in blue light materials. The pure organic thermally activated delayed fluorescence (TADF) material has a molecular structure combining electron donor (D) and electron acceptor (A). Through clever molecular design, the molecule has a small minimum single triplet energy difference (ΔE) ST ), so that the triplet excitons can return to the singlet state through the reverse intersystem crossing (RISC), and then through the radiation transition to the ground state to emit light, so that the singlet and triplet excitons can be used at the same time, and 100% can also be achieved IQE.
对于TADF材料，快速的反向系间窜越常数(k RISC)以及高的光致发光量子产率(PLQY)是制备高效率OLED器件的必要条件。目前，具备上述条件的TADF材料相对于重金属Ir配合物而言还是比较匮乏。 For TADF materials, fast reverse intersystem crossing constant (k RISC ) and high photoluminescence quantum yield (PLQY) are necessary conditions for the preparation of high-efficiency OLED devices. At present, TADF materials with the above conditions are still relatively scarce compared to heavy metal Ir complexes.
发明内容Summary of the invention
本发明的目的在于提供一种热活化延迟荧光材料，具有超快反向系间窜越速率及高发光效率，为具有显著TADF特性的TADF化合物，可作为有机电致发光二极管的发光层客体材料。The purpose of the present invention is to provide a thermally activated delayed fluorescent material, which has an ultra-fast reverse inter-system crossing rate and high luminous efficiency, is a TADF compound with significant TADF characteristics, and can be used as a guest material for the light-emitting layer of an organic electroluminescent diode .
本发明另一目的在于提供一种热活化延迟荧光材料的制备方法，该方法易于操作，且获得目标产物的产率较高。Another object of the present invention is to provide a method for preparing a thermally activated delayed fluorescent material, which is easy to operate and has a high yield of the target product.
本发明又一目的在于提供一种有机电致发光二极管器件，采用上述热活化延迟荧光材料作为发光层客体材料，从而提高器件的发光效率。Another object of the present invention is to provide an organic electroluminescent diode device, which uses the thermally activated delayed fluorescent material as the guest material of the light-emitting layer, thereby improving the light-emitting efficiency of the device.
为实现上述发明目的，本发明提供一种热活化延迟荧光材料，具有如下式一所示的化学结构：In order to achieve the above-mentioned object of the invention, the present invention provides a thermally activated delayed fluorescent material, which has a chemical structure shown in the following formula 1:
式一Formula one
Figure PCTCN2019085649-appb-000001
Figure PCTCN2019085649-appb-000001
以上式一中，R 1表示作为电子给体的化学基团，R 2表示作为电子受体的化学基团。 In the above formula 1, R 1 represents a chemical group as an electron donor, and R 2 represents a chemical group as an electron acceptor.
所述电子给体基团R 1选自以下基团中的任意一种： The electron donor group R 1 is selected from any one of the following groups:
Figure PCTCN2019085649-appb-000002
Figure PCTCN2019085649-appb-000002
所述电子受体基团R 2选自以下基团中的任意一种： The electron acceptor group R 2 is selected from any one of the following groups:
Figure PCTCN2019085649-appb-000003
Figure PCTCN2019085649-appb-000003
所述的热活化延迟荧光材料为化合物1、化合物2或化合物3，所述化合物1、化合物2和化合物3的结构式分别如下：The thermally activated delayed fluorescent material is compound 1, compound 2 or compound 3. The structural formulas of compound 1, compound 2 and compound 3 are as follows:
Figure PCTCN2019085649-appb-000004
Figure PCTCN2019085649-appb-000004
本发明还提供一种热活化延迟荧光材料的制备方法，其化学合成路线如下：The present invention also provides a method for preparing thermally activated delayed fluorescent material, and its chemical synthesis route is as follows:
Figure PCTCN2019085649-appb-000005
Figure PCTCN2019085649-appb-000005
具体为：向反应瓶中加入摩尔比为1:1-2:0.02-0.1:0.1-0.29的卤代原料、含电子给体化合物、醋酸钯和三叔丁基膦四氟硼酸盐，然后在无水无氧环境下按与卤代原料为1-2：1的摩尔比加入叔丁醇钠，在氩气氛围下打入除水除氧的甲苯，在110-130℃反应20-30小时；冷却至室温，将反应液倒入冰水中，萃取后合并有机相，旋成硅胶，柱层析分离纯化，得产物，计算收率；Specifically: add halogenated raw materials, electron donor compounds, palladium acetate and tri-tert-butylphosphine tetrafluoroborate with a molar ratio of 1:1-2:0.02-0.1:0.1-0.29 to the reaction flask, and then In an anhydrous and oxygen-free environment, add sodium tert-butoxide at a molar ratio of 1-2:1 to the halogenated raw materials. In an argon atmosphere, drive in toluene for removing water and oxygen, and react at 110-130℃ for 20-30 Hours; cool to room temperature, pour the reaction solution into ice water, combine the organic phases after extraction, spin into silica gel, separate and purify by column chromatography to obtain the product, calculate the yield;
所述卤代原料的结构通式为
Figure PCTCN2019085649-appb-000006
其中，X为卤素基团，R 2表示作为电子受体的化学基团； The general structural formula of the halogenated raw material is
Figure PCTCN2019085649-appb-000006
Wherein, X is a halogen group, and R 2 represents a chemical group as an electron acceptor;
所述含电子给体化合物的结构通式为R 1-H，其中，R 1表示作为电子给 体的化学基团。 The general structural formula of the electron-donor-containing compound is R 1 -H, wherein R 1 represents a chemical group as an electron donor.
所述电子给体基团R 1选自以下基团中的任意一种： The electron donor group R 1 is selected from any one of the following groups:
Figure PCTCN2019085649-appb-000007
Figure PCTCN2019085649-appb-000007
所述电子受体基团R 2选自以下基团中的任意一种： The electron acceptor group R 2 is selected from any one of the following groups:
Figure PCTCN2019085649-appb-000008
Figure PCTCN2019085649-appb-000008
所述卤代原料的结构式为
Figure PCTCN2019085649-appb-000009
The structural formula of the halogenated raw material is
Figure PCTCN2019085649-appb-000009
所述含电子给体化合物为9,10-二氢-9,9-二甲基吖啶、吩噁嗪或吩噻嗪。The electron donor compound is 9,10-dihydro-9,9-dimethylacridine, phenoxazine or phenothiazine.
本发明还提供一种有机电致发光二极管器件，包括基板、设置于所述基板上的第一电极、设置于第一电极上的有机功能层及设置于所述有机功能层上的第二电极；The present invention also provides an organic electroluminescent diode device, including a substrate, a first electrode provided on the substrate, an organic functional layer provided on the first electrode, and a second electrode provided on the organic functional layer ；
所述有机功能层包括一层或多层有机膜层，且至少一层所述有机膜层为发光层；The organic functional layer includes one or more organic film layers, and at least one of the organic film layers is a light-emitting layer;
所述发光层包含混合的主体材料与客体材料，所述客体材料选自如上 所述的热活化延迟荧光材料中的一种或多种。The light-emitting layer includes a mixed host material and a guest material, and the guest material is selected from one or more of the thermally activated delayed fluorescent materials as described above.
所述发光层采用真空蒸镀或者溶液涂覆的方法形成。The light-emitting layer is formed by vacuum evaporation or solution coating.
所述主体材料为mCBP。The host material is mCBP.
所述基板为玻璃基板，所述第一电极的材料为氧化铟锡，所述第二电极为氟化锂层与铝层构成的双层复合结构；The substrate is a glass substrate, the material of the first electrode is indium tin oxide, and the second electrode is a double-layer composite structure composed of a lithium fluoride layer and an aluminum layer;
所述有机功能层包括多层有机膜层，该多层有机膜层包括空穴注入层、空穴传输层、发光层、电子传输层，其中，所述空穴注入层的材料为三氧化钼，所述空穴传输层的材料为TCTA，所述电子传输层的材料为TmPyPB。The organic functional layer includes multiple organic film layers, the multilayer organic film layer includes a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, wherein the material of the hole injection layer is molybdenum trioxide The material of the hole transport layer is TCTA, and the material of the electron transport layer is TmPyPB.
相比于已有材料和技术，本发明具有如下优点和有益效果：Compared with existing materials and technologies, the present invention has the following advantages and beneficial effects:
(1)本发明通过对电子给体基团的结构微调，使得它们具有不同的给电子能力，设计出具有显著TADF特性的热活化延迟荧光材料，实现了材料发光光谱从从橙红光到深红光范围内的微调；(1) In the present invention, by fine-tuning the structure of the electron donor groups to make them have different electron donating abilities, a thermally activated delayed fluorescent material with significant TADF characteristics is designed, and the luminescence spectrum of the material is changed from orange-red light to deep red Fine adjustment in the light range;
(2)本发明的热活化延迟荧光材料，为具有较低单三线态能级差、超快反向系间窜越速率及高发光效率的红光TADF化合物，当其作为红光客体材料应用于有机发光显示装置时，可以提高有机发光显示装置的发光效率，基于本发明的热活化延迟荧光材料的有机电致发光二极管器件都取得了非常高的器件效率。(2) The thermally activated delayed fluorescent material of the present invention is a red TADF compound with lower single triplet energy level difference, ultrafast reverse intersystem crossing rate and high luminous efficiency, when it is used as a red light guest material In the case of an organic light-emitting display device, the light-emitting efficiency of the organic light-emitting display device can be improved. The organic electroluminescent diode device based on the thermally activated delayed fluorescent material of the present invention has achieved very high device efficiency.
附图说明Description of the drawings
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。The technical solutions and other beneficial effects of the present invention will be made obvious by describing in detail the specific embodiments of the present invention in conjunction with the accompanying drawings.
附图中，In the attached picture,
图1为本发明具体实施例1-3中所制备的化合物1-3的HOMO与LUMO能级分布图；Figure 1 is a diagram of HOMO and LUMO energy levels of compounds 1-3 prepared in specific examples 1-3 of the present invention;
图2为本发明具体实施例1-3中所制备的化合物1-3在室温下甲苯溶液中的光致发光光谱图；Figure 2 is a photoluminescence spectrum of compound 1-3 prepared in specific examples 1-3 of the present invention in a toluene solution at room temperature;
图3为本发明有机电致发光二极管器件的结构示意图。Fig. 3 is a schematic diagram of the structure of the organic electroluminescent diode device of the present invention.
具体实施方式detailed description
本发明中所用的未注明的一些原料均为市售商品。一些化合物的制备方法将在实施案例中描述。下面结合具体实施例对本发明作进一步具体详细描述，但本发明的实施方式不限于此。Some unspecified raw materials used in the present invention are all commercially available products. The preparation methods of some compounds will be described in the implementation case. The present invention will be further described in detail below in conjunction with specific examples, but the implementation of the present invention is not limited thereto.
实施例1：Example 1:
目标化合物1的合成路线如下：The synthetic route of target compound 1 is as follows:
Figure PCTCN2019085649-appb-000010
Figure PCTCN2019085649-appb-000010
向100mL二口瓶中加入原料1(2.68g，5mmol)，9,10-二氢-9,9-二甲基吖啶(1.25g，6mmol)，醋酸钯Pb(OAc)(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(t-Bu) 3HPBF 4(0.17g，0.6mmol)，然后在手套箱中加入叔丁醇钠NaOt-Bu(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应24小时。冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，3:1)分离纯化，得1.7g橙红色粉末的化合物1，产率55％。 Add raw material 1 (2.68g, 5mmol), 9,10-dihydro-9,9-dimethylacridine (1.25g, 6mmol), palladium acetate Pb(OAc) (45mg, 0.2mmol) into a 100mL two-neck flask ) And tri-tert-butylphosphine tetrafluoroborate (t-Bu) 3 HPBF 4 (0.17g, 0.6mmol), and then add sodium tert-butoxide NaOt-Bu (0.58g, 6mmol) in the glove box. 40 mL of toluene that had been dewatered and deoxygenated was injected under an air atmosphere, and reacted at 120°C for 24 hours. Cool to room temperature, pour the reaction solution into 200 mL ice water, extract three times with dichloromethane, combine the organic phases, spin into silica gel, and separate and purify by column chromatography (dichloromethane: n-hexane, v: v, 3:1) to obtain 1.7 g of compound 1 as orange-red powder, with a yield of 55%.
1HNMR(300MHz,CD 2Cl 2,δ):8.74(s,4H),7.62-7.50(m,5H),7.20-7.14(m,6H),6.95-6.90(m,2H),1.69(s,6H)。 1HNMR (300MHz, CD 2 Cl 2 , δ): 8.74 (s, 4H), 7.62-7.50 (m, 5H), 7.20-7.14 (m, 6H), 6.95-6.90 (m, 2H), 1.69 (s, 6H).
实施例2：Example 2:
目标化合物2的合成路线如下：The synthetic route of target compound 2 is as follows:
Figure PCTCN2019085649-appb-000011
Figure PCTCN2019085649-appb-000011
向100mL二口瓶中加入原料1(2.68g，5mmol)，吩噁嗪(1.10g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入叔丁醇钠(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应24小时。冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，3:1)分离纯化，得1.6g红色粉末的化合物2，产率54％。To a 100mL two-neck flask was added raw material 1 (2.68g, 5mmol), phenoxazine (1.10g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6 mmol), and then add sodium tert-butoxide (0.58 g, 6 mmol) into the glove box, and drive 40 mL of toluene previously dewatered and deoxygenated under an argon atmosphere, and react at 120° C. for 24 hours. Cool to room temperature, pour the reaction solution into 200 mL ice water, extract three times with dichloromethane, combine the organic phases, spin into silica gel, and separate and purify by column chromatography (dichloromethane: n-hexane, v: v, 3:1) to obtain 1.6 g of compound 2 as a red powder, with a yield of 54%.
1H NMR(300MHz,CD 2Cl 2,δ):8.74(s,4H),7.62-7.50(m,5H),7.19-7.14 (m,2H),7.05-6.96(m,6H)。 1 H NMR (300 MHz, CD 2 Cl 2 , δ): 8.74 (s, 4H), 7.62-7.50 (m, 5H), 7.19-7.14 (m, 2H), 7.05-6.96 (m, 6H).
实施例3：Example 3:
目标化合物3的合成路线如下所示：The synthetic route of target compound 3 is as follows:
Figure PCTCN2019085649-appb-000012
Figure PCTCN2019085649-appb-000012
向100mL二口瓶中加入原料1(2.68g，5mmol)，吩噻嗪(1.19g，6mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入叔丁醇钠(0.58g，6mmol)，在氩气氛围下打入40mL事先除水除氧的甲苯，在120℃反应24小时。冷却至室温，将反应液倒入200mL冰水中，二氯甲烷萃取三次，合并有机相，旋成硅胶，柱层析(二氯甲烷:正己烷，v:v，3:1)分离纯化，得1.1g深红色粉末的化合物3，产率36％。To a 100mL two-neck flask was added raw material 1 (2.68g, 5mmol), phenothiazine (1.19g, 6mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine tetrafluoroborate (0.17g, 0.6 mmol), and then add sodium tert-butoxide (0.58 g, 6 mmol) into the glove box, and drive 40 mL of toluene previously dewatered and deoxygenated under an argon atmosphere, and react at 120° C. for 24 hours. Cool to room temperature, pour the reaction solution into 200 mL ice water, extract three times with dichloromethane, combine the organic phases, spin into silica gel, and separate and purify by column chromatography (dichloromethane: n-hexane, v: v, 3:1) to obtain 1.1 g of compound 3 as a dark red powder with a yield of 36%.
1H NMR(300MHz,CD 2Cl 2,δ):8.74(s,4H),7.62-7.50(m,5H),7.20-7.14(m,6H),6.96-6.89(m,2H)。 1 H NMR (300MHz, CD 2 Cl 2 , δ): 8.74 (s, 4H), 7.62-7.50 (m, 5H), 7.20-7.14 (m, 6H), 6.96-6.89 (m, 2H).
图1示出了化合物1-3的轨道排布情况，从图1中可以明显看出，化合物1-3的最高电子占据轨道(HOMO)与最低电子未占据轨道(LUMO)均分别排布在不同的单元上，实现了完全的分离，这有助于减小系间能差ΔEST，从而提高反向系间窜越能力。图2示出了化合物1-3在室温下甲苯溶液中的光致发光光谱。针对化合物1-3，模拟计算了分子的最低单线态能级S1和最低三线态能级T1。Figure 1 shows the orbital arrangement of compound 1-3. It can be clearly seen from Figure 1 that the highest electron occupied orbital (HOMO) and lowest electron unoccupied orbital (LUMO) of compound 1-3 are arranged in In different units, complete separation is achieved, which helps to reduce the energy difference ΔEST between systems, thereby improving the ability of reverse intersystem crossing. Figure 2 shows the photoluminescence spectra of Compound 1-3 in a toluene solution at room temperature. For compounds 1-3, the lowest singlet energy level S1 and the lowest triplet energy level T1 of the molecule were simulated and calculated.
实施例1-3的相关数据如表1所示。由表1可以看出，所有化合物的ΔEst均小于0.3ev，实现了较小的单线态和三线态能级差，具有明显的延迟荧光效应。The relevant data of Examples 1-3 are shown in Table 1. It can be seen from Table 1 that the ΔEst of all the compounds is less than 0.3ev, which achieves a small singlet and triplet energy level difference, and has an obvious delayed fluorescence effect.
表1、化合物1-3的光物理性质结果Table 1. Results of photophysical properties of compounds 1-3
Figure PCTCN2019085649-appb-000013
Figure PCTCN2019085649-appb-000013
表1中，PL Peak表示光致发光峰，S1表示单线态能级，T1表示三线态能级，ΔEST表示单线态和三线态能级差。In Table 1, PL Peak represents the photoluminescence peak, S1 represents the singlet energy level, T1 represents the triplet energy level, and ΔEST represents the difference between the singlet and triplet energy levels.
实施例4：Example 4:
有机电致发光二极管(OLED)器件的制备：Preparation of organic electroluminescent diode (OLED) devices:
如图1所述，本发明的热活化延迟荧光材料作为发光层客体材料的有机电致发光二极管器件，可包括从下到上依次设置的基板9、阳极层1、空穴注入层2、空穴传输层3、发光层4、电子传输层5、及阴极层6。其中，所述基板9为玻璃基板，所述阳极1的材料为氧化铟锡(ITO)，所述基板9与阳极1共同构成ITO玻璃。所述空穴注入层2的材料为三氧化钼(MoO 3)，所述空穴传输层3的材料为TCTA，所述发光层的材料为本发明的活化延迟荧光化合物与mCBP的混合物，所述电子传输层5的材料为TmPyPB。所述阴极为氟化锂(LiF)层与铝(Al)层构成的双层结构。 As shown in Fig. 1, the organic electroluminescent diode device using the thermally activated delayed fluorescent material of the present invention as the guest material of the light-emitting layer may include a substrate 9, an anode layer 1, a hole injection layer 2, and a cavity which are sequentially arranged from bottom to top. Hole transport layer 3, light emitting layer 4, electron transport layer 5, and cathode layer 6. Wherein, the substrate 9 is a glass substrate, the material of the anode 1 is indium tin oxide (ITO), and the substrate 9 and the anode 1 together constitute ITO glass. The material of the hole injection layer 2 is molybdenum trioxide (MoO 3 ), the material of the hole transport layer 3 is TCTA, and the material of the light-emitting layer is a mixture of the activated delayed fluorescent compound of the present invention and mCBP. The material of the electron transport layer 5 is TmPyPB. The cathode has a double-layer structure composed of a lithium fluoride (LiF) layer and an aluminum (Al) layer.
其中，TCTA指4,4',4”-三(咔唑-9-基)三苯胺，mCBP指3,3'-二(N-咔唑基)-1,1'-联苯，TmPyPB指1,3,5-三(3-(3-吡啶基)苯基)苯。Among them, TCTA refers to 4,4',4”-tris(carbazol-9-yl)triphenylamine, mCBP refers to 3,3'-bis(N-carbazolyl)-1,1'-biphenyl, and TmPyPB refers to 1,3,5-Tris(3-(3-pyridyl)phenyl)benzene.
所述有机电致发光二极管器件可按本领域已知方法制作，具体方法为：在经过清洗的ITO玻璃上，高真空条件下依次蒸镀2nm厚的MoO 3膜、35nm厚的TCTA膜、mCBP加活化延迟荧光化合物、40nm厚的TmPyPB膜、1nm厚的LiF膜和100nm厚的Al膜。用该方法制得如图3所示的器件，各种具体的器件结构如下： The organic electroluminescent diode device can be manufactured according to a method known in the art, and the specific method is: sequentially vapor-depositing a 2nm thick MoO 3 film, a 35nm thick TCTA film, and mCBP on the cleaned ITO glass under high vacuum conditions Add activated delayed fluorescent compound, 40nm thick TmPyPB film, 1nm thick LiF film and 100nm thick Al film. The device as shown in Figure 3 is made by this method, and the specific device structures are as follows:
器件1：Device 1:
ITO/MoO 3(2nm)/TCTA(35nm)/mCBP：化合物1(20％40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm) ITO/MoO 3 (2nm)/TCTA(35nm)/mCBP: Compound 1(20%40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
器件2：Device 2:
ITO/MoO 3(2nm)/TCTA(35nm)/mCBP：化合物2(20％40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm) ITO/MoO 3 (2nm)/TCTA(35nm)/mCBP: Compound 2(20%40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
器件3：Device 3:
ITO/MoO 3(2nm)/TCTA(35nm)/mCBP：化合物3(20％40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm) ITO/MoO 3 (2nm)/TCTA(35nm)/mCBP: Compound 3(20%40nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm)
器件1-3的电流-亮度-电压特性是由带有校正过的硅光电二极管的Keithley源测量***(Keithley 2400Sourcemeter、Keithley 2000Currentmeter)完成的，电致发光光谱是由法国JY公司SPEX CCD3000光谱仪测量的，所有测量均在室温大气中完成。器件1-3的性能数据见下表2。The current-brightness-voltage characteristics of devices 1-3 are completed by Keithley source measurement systems (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes, and the electroluminescence spectrum is measured by the French JY company SPEX CCD3000 spectrometer , All measurements are done in room temperature atmosphere. The performance data of devices 1-3 are shown in Table 2 below.
表2、基于化合物1-3为发光层客体材料的器件的性能结果Table 2. Performance results of devices based on compounds 1-3 as guest materials for the light-emitting layer
Figure PCTCN2019085649-appb-000014
Figure PCTCN2019085649-appb-000014
表2中，CIEy为标准CIE色彩空间的y坐标值。In Table 2, CIEy is the y coordinate value of the standard CIE color space.
综上所述，本发明通过对电子给体的结构微调，改变电子给体的给电子能力，研究电子给体的强弱对材料性能带来的影响，设计出具有显著TADF特性的热活化延迟荧光材料，实现了材料发光光谱从从橙红光到深红光范围内的调节；本发明进一步将上述热活化延迟荧光材料应用于有机电致发光二极管器件的客体材料时，可以有效提高有机电致发光二极管器件的发光效率，基于本发明的热活化延迟荧光材料的有机电致发光二极管器件具有非常高的器件效率。In summary, the present invention fine-tunes the structure of the electron donor, changes the electron donating ability of the electron donor, studies the influence of the strength of the electron donor on the material performance, and designs a thermal activation delay with significant TADF characteristics. The fluorescent material realizes the adjustment of the luminescence spectrum of the material from orange-red light to deep red light; when the present invention further applies the thermally activated delayed fluorescent material to the guest material of an organic electroluminescent diode device, it can effectively improve the organic electroluminescence The luminous efficiency of the light-emitting diode device, the organic electroluminescent diode device based on the thermally activated delayed fluorescent material of the present invention has a very high device efficiency.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, etc. made without departing from the spirit and principle of the present invention Simplified, all should be equivalent replacement methods, and they are all included in the protection scope of the present invention.

Claims (10)

  1. 一种热活化延迟荧光材料，具有如下式一所示的化学结构：A thermally activated delayed fluorescent material has a chemical structure shown in the following formula 1:
    式一Formula one
    Figure PCTCN2019085649-appb-100001
    Figure PCTCN2019085649-appb-100001
    以上式一中，R 1表示作为电子给体的化学基团，R 2表示作为电子受体的化学基团。 In the above formula 1, R 1 represents a chemical group as an electron donor, and R 2 represents a chemical group as an electron acceptor.
  2. 如权利要求1所述的热活化延迟荧光材料，其中，所述电子给体的化学基团R 1选自以下基团中的任意一种： The thermally activated delayed fluorescent material according to claim 1, wherein the chemical group R 1 of the electron donor is selected from any one of the following groups:
    Figure PCTCN2019085649-appb-100002
    Figure PCTCN2019085649-appb-100002
    所述电子受体的化学基团R 2选自以下基团中的任意一种： The chemical group R 2 of the electron acceptor is selected from any one of the following groups:
    Figure PCTCN2019085649-appb-100003
    Figure PCTCN2019085649-appb-100003
  3. 如权利要求2所述的热活化延迟荧光材料，为化合物1、化合物2或化合物3，所述化合物1、化合物2和化合物3的结构式分别如下：The thermally activated delayed fluorescent material of claim 2 is compound 1, compound 2, or compound 3. The structural formulas of compound 1, compound 2 and compound 3 are as follows:
    Figure PCTCN2019085649-appb-100004
    Figure PCTCN2019085649-appb-100004
  4. 一种热活化延迟荧光材料的制备方法，化学合成路线如下：A preparation method of thermally activated delayed fluorescent material, the chemical synthesis route is as follows:
    Figure PCTCN2019085649-appb-100005
    Figure PCTCN2019085649-appb-100005
    具体为：向反应瓶中加入摩尔比为1:1-2:0.02-0.1:0.1-0.29的卤代原料、含电子给体化合物、醋酸钯和三叔丁基膦四氟硼酸盐，然后在无水无氧环境下按与卤代原料为1-2：1的摩尔比加入叔丁醇钠，在氩气氛围下打入除水除氧的甲苯，在110-130℃反应20-30小时；冷却至室温，将反应液倒入冰水中，萃取后合并有机相，旋成硅胶，柱层析分离纯化，得产物，计算收率；Specifically: add halogenated raw materials, electron donor compounds, palladium acetate and tri-tert-butylphosphine tetrafluoroborate with a molar ratio of 1:1-2:0.02-0.1:0.1-0.29 to the reaction flask, and then In an anhydrous and oxygen-free environment, add sodium tert-butoxide at a molar ratio of 1-2:1 to the halogenated raw materials. In an argon atmosphere, drive in toluene for removing water and oxygen, and react at 110-130℃ for 20-30 Hours; cool to room temperature, pour the reaction solution into ice water, combine the organic phases after extraction, spin into silica gel, separate and purify by column chromatography to obtain the product, calculate the yield;
    所述卤代原料的结构通式为
    Figure PCTCN2019085649-appb-100006
    其中，X为卤素基团，R 2表示作为电子受体的化学基团；     The general structural formula of the halogenated raw material is
    Figure PCTCN2019085649-appb-100006
    Wherein, X is a halogen group, and R 2 represents a chemical group as an electron acceptor;
    所述含电子给体化合物的结构通式为R 1-H，其中，R 1表示作为电子给体的化学基团。 The general structural formula of the electron-donor-containing compound is R 1 -H, wherein R 1 represents a chemical group as an electron donor.
  5. 如权利要求4所述的热活化延迟荧光材料的制备方法，其中，所述电子给体的化学基团R 1选自以下基团中的任意一种： The method for preparing a thermally activated delayed fluorescent material according to claim 4, wherein the chemical group R 1 of the electron donor is selected from any one of the following groups:
    Figure PCTCN2019085649-appb-100007
    Figure PCTCN2019085649-appb-100007
    所述电子受体的化学基团R 2选自以下基团中的任意一种： The chemical group R 2 of the electron acceptor is selected from any one of the following groups:
    Figure PCTCN2019085649-appb-100008
    Figure PCTCN2019085649-appb-100008
  6. 如权利要求5所述的热活化延迟荧光材料的制备方法，其中，所述卤代原料的结构式为
    Figure PCTCN2019085649-appb-100009
    The method for preparing a thermally activated delayed fluorescent material according to claim 5, wherein the structural formula of the halogenated raw material is
    Figure PCTCN2019085649-appb-100009
    所述含电子给体化合物为9,10-二氢-9,9-二甲基吖啶、吩噁嗪或吩噻嗪。The electron donor compound is 9,10-dihydro-9,9-dimethylacridine, phenoxazine or phenothiazine.
  7. 一种有机电致发光二极管器件，包括基板、设置于所述基板上的第一电极、设置于第一电极上的有机功能层及设置于所述有机功能层上的第二电极；An organic electroluminescent diode device, comprising a substrate, a first electrode provided on the substrate, an organic functional layer provided on the first electrode, and a second electrode provided on the organic functional layer;
    所述有机功能层包括一层或多层有机膜层，且至少一层所述有机膜层为发光层；The organic functional layer includes one or more organic film layers, and at least one of the organic film layers is a light-emitting layer;
    所述发光层包含混合的主体材料与客体材料，所述客体材料选自如权利要求1所述的热活化延迟荧光材料中的一种或多种。The light-emitting layer comprises a mixed host material and a guest material, and the guest material is selected from one or more of the thermally activated delayed fluorescent materials according to claim 1.
  8. 如权利要求7所述的有机电致发光二极管器件，其中，所述发光层采用真空蒸镀或者溶液涂覆的方法形成。8. The organic electroluminescent diode device of claim 7, wherein the light-emitting layer is formed by vacuum evaporation or solution coating.
  9. 如权利要求7所述的有机电致发光二极管器件，其中，所述主体材料为mCBP。8. The organic electroluminescent diode device of claim 7, wherein the host material is mCBP.
  10. 如权利要求7所述的有机电致发光二极管器件，其中，所述基板为玻璃基板，所述第一电极的材料为氧化铟锡，所述第二电极为氟化锂层与铝层构成的双层复合结构；The organic electroluminescent diode device of claim 7, wherein the substrate is a glass substrate, the material of the first electrode is indium tin oxide, and the second electrode is composed of a lithium fluoride layer and an aluminum layer Double-layer composite structure;
    所述有机功能层包括多层有机膜层，该多层有机膜层包括空穴注入层、空穴传输层、发光层、电子传输层，其中，所述空穴注入层的材料为三氧化钼，所述空穴传输层的材料为TCTA，所述电子传输层的材料为TmPyPB。The organic functional layer includes multiple organic film layers, the multilayer organic film layer includes a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, wherein the material of the hole injection layer is molybdenum trioxide The material of the hole transport layer is TCTA, and the material of the electron transport layer is TmPyPB.
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